Composition for the oxidation dyeing of keratin fibres, comprising at least one 4,5- or 3,4-diaminopyrazole or a triaminopyrazole and at least one selected mineral compound, and dyeing process

ABSTRACT

The present invention relates to a composition for the oxidation dyeing of keratin fibers, in particular of human keratin fibers such as the hair, comprising at least one oxidation base chosen from 4,5- or 3,4-diaminopyrazoles and triaminopyrazoles, in combination with at least one selected mineral compound, and also to the dyeing process using this composition with an oxidizing agent.

The present invention relates to a composition for the oxidation dyeingof keratin fibres, in particular of human keratin fibres such as thehair, comprising at least one oxidation base chosen from 4,5- or3,4-diaminopyrazoles and triaminopyrazoles, in combination with at leastone selected mineral compound, and also to the dyeing process using thiscomposition with an oxidizing agent.

It is known practice to dye keratin fibres, and in particular humanhair, with dye compositions containing oxidation dye precursors, inparticular ortho- or para-phenylenediamines, ortho- or para-aminophenolsor heterocyclic compounds such as pyrazole derivatives which aregenerally referred to as oxidation bases. Oxidation dye precursors, oroxidation bases, are colourless or weakly coloured compounds which, whencombined with oxidizing products, can give rise to coloured compoundsand dyes by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases canbe varied by combining them with suitably selected couplers orcoloration modifiers, the latter being chosen in particular fromaromatic meta-diamines, meta-aminophenols, meta-diphenols and certainheterocyclic compounds.

The variety of molecules used as regards the oxidation bases and thecouplers allows a wide range of colours to be obtained.

The “permanent” coloration obtained by means of these oxidation dyesmust moreover satisfy a certain number of requirements. Thus it must nothave any toxicological disadvantages, it must be able to give shades ofthe desired intensity and it must be able to withstand external agents(light, bad weather, washing, permanent-waving, perspiration, rubbing).

The dyes must also be able to cover white hair and, lastly, they must beas unselective as possible, i.e. they must give the smallest possiblecolour differences along the same length of keratin fibre, which may infact be differently sensitized (i.e. damaged) between its end and itsroot.

Compositions for the oxidation dyeing of keratin fibres, containingpyrazole derivatives such as 4,5-diaminopyrazoles, 3,4-diaminopyrazolesor 3,4,5-triaminopyrazoles as oxidation base have already been proposed,especially in German patent applications DE 3 843 892, DE 4 234 887, DE4 234 886, DE 4 234 885 or DE 195 43 988. However, such compositions arenot entirely satisfactory since, during the dyeing processes, sidereactions take place that can have adverse effects in terms of theharmlessness and of the dyeing properties obtained, and especially thestrength and resistance of the colorations with respect to the variousattacking factors to which the hair may be subjected.

Compositions for the oxidation dyeing of keratin fibres, comprising acombination of an oxidation base of the 4,5-diaminopyrazole type, a zincsalt and a derivative of 1,4-diazacycloheptane or a salt thereof, havingthe following formula:

in which R¹, R², R³ and R⁴, which may be identical or different, denotea hydrogen, a C₁–C₄ alkyl or hydroxyalkyl, or a C₂–C₄ dihydroxyalkyl;Z¹ and Z², which may be identical or different, denote hydrogen,chlorine, fluorine, a C₁–C₄ alkyl, a C₁–C₄ hydroxyalkyl, a C₁–C₄aminoalkyl, a C₁–C₄ alkoxy, a C₂–C₄ dihydroxyalkyl or an allyl group;R⁵ and R⁶, which may be identical or different, denote a hydrogen or aC₁–C₄ alkyl,are also known in patent application WO 01/34104.

The aim of the invention is to develop novel dye compositions that donot have the drawbacks of the dyes of the prior art, in particularstrong dyes that are particularly resistant to the various attackingfactors to which the hair may be subjected, and that show goodharmlessness.

To this end, one subject of the invention is a composition for theoxidation dyeing of human keratin fibres, and in particular of humankeratin fibres such as the hair, comprising, in a medium that issuitable for dyeing:

-   at least one oxidation base chosen from 4,5- or 3,4-diaminopyrazoles    and triaminopyrazoles, and-   at least one mineral compound chosen from silicas, aluminium oxides    or hydroxides, aluminium, magnesium or iron hydrosilicates alone or    as a mixture, and zinc salts;    the said composition not containing a combination of an oxidation    base of the 4,5-diaminopyrazole type, a zinc salt and a derivative    of 1,4-diazacycloheptane or a salt thereof, having the following    formula:

in which R¹, R², R³ and R⁴, which may be identical or different, denotea hydrogen, a C₁–C₄ alkyl or hydroxy-alkyl, or a C₂–C₄ dihydroxyalkyl;Z¹ and Z², which may be identical or different, denote hydrogen,chlorine, fluorine, a C₁–C₄ alkyl, a C₁–C₄ hydroxyalkyl, a C₁–C₄aminoalkyl, a C₁–C₄ alkoxy, a C₂–C₄ dihydroxyalkyl or an allyl group;R⁵ and R⁶, which may be identical or different, denote a hydrogen or aC₁–C₄ alkyl.

The oxidation dye composition of the invention makes it possible toobtain, with good harmlessness, strong, relatively unselectivecolorations in varied shades, which show excellent resistance propertiesboth with respect to atmospheric agents such as light and bad weatherand with respect to perspiration and various treatments to which thehair may be subjected (shampooing or permanent reshaping).

Except where otherwise mentioned, all the radicals, substituents, groupsand chains in the context of the invention are linear or branched, andsubstituted or unsubstituted.

Among the silicas that are useful in the composition of the invention,mention may be made of crystalline, microcrystalline and non-crystallinesilicas.

By way of example, crystalline silicas that may be mentioned includequartz, tridymite, cristobalite, keatite, coesite and stishovite. Themicrocrystalline silicas are, for example, diatomite.

Among the non-crystalline forms that may be used are vitreous silica andother types of amorphous silicas such as colloidal silicas, silica gels,precipitated silicas and fumed silicas, for instance aerosils, andpyrogenic silicas.

Among the aluminium hydroxides that may be used according to theinvention, mention may be made of compounds having the compositionAl(OH)₃, such as the α-alumina trihydrate hydragillite or gibbsite orthe β-alumina trihydrate bayerite, and compounds having the compositionAlOOH, such as the new β-trihydrate nordstrandite, the α-aluminamonohydrate boehmite and the β-alumina monohydrate diaspore.

Among the aluminium oxides that may be used according to the invention,mention may be made of activated aluminas whose crystal structure isthat of the γ, η, χ or ρ transition aluminas, or the calcined aluminassuch as α alumina. Mention may also be made of β aluminas such as sodiumβ-aluminates, sodium γ-aluminates, sodium β-aluminas, potassiumβ-aluminas, magnesium β-aluminas, calcium β-aluminas, strontiumβ-aluminas, barium β-aluminas and lithium ξ-aluminas.

Among the aluminium hydrosilicates that may be mentioned are kaolinite,dicktite, nacrite and halloysite-endellite found in clays of kaolintype, and also pyrophyllite and beidellite found in smectites.

Among the magnesium hydrosilicates that may be mentioned are talc, whichis found in smectites, and serpentines such as chrysotile.

Among the hydrosilicates containing several of the above metal elements,mention may be made of montmorillonite and saponite(aluminium+magnesium), nontronite (aluminium+iron) and sauconite(aluminium+magnesium+iron) which are found in smectites, and amesite(aluminium+magnesium), chamosite and illite (iron+aluminium+magnesium).

Among the zinc salts that may be mentioned are the salts obtained with amineral acid, for instance the sulphate, hydrochloride, nitrate,carbonate, hydrogen carbonate, orthophosphate, ortho-hydrogen phosphateand ortho-dihydrogen phosphate, and the salts obtained with organicacids, for instance the tartrate, citrate, acetate or lactate.

The mineral compound(s) preferably represent(s) from 0.00001% to 10% byweight and even more preferably from 0.001% to 5% by weightapproximately relative to the total weight of the dye composition, andeven more preferentially from 0.001% to 3% by weight approximatelyrelative to this weight.

Among the 4,5- or 3,4-diaminopyrazoles that are useful in the dyecompositions of the invention, mention may be made particularly of thediaminopyrazoles chosen from the 4,5- or 3,4-diaminopyrazoles of formula(I) or (II) below, and/or the addition salts thereof with an acid:

in which:

-   R₁, R₂, R₃, R₄ and R₅, which may be identical or different,    represent a hydrogen atom; a C₁–C₆ alkyl radical which is    unsubstituted or substituted with at least one substituent chosen    from OR, NHR, NRR′, SR, SOR, SO₂R, COR, COOH, CONH₂, CONHR, CONRR′,    PO(OH)₂, SH and SO₃X, a non-cationic heterocycle, Cl, Br or I, X    denoting a hydrogen atom, Na, K or NH₄, and R and R′, which may be    identical or different, representing a C₁–C₄ alkyl or alkenyl; a    C₂–C₄ hydroxyalkyl radical; a C₂–C₄ aminoalkyl radical; a phenyl    radical; a phenyl radical substituted with a halogen atom or a C₁–C₄    alkyl, C₁–C₄ alkoxy, nitro, trifluoromethyl, amino or C₁–C₄    alkylamino radical; a benzyl radical; a benzyl radical substituted    with a halogen atom or with a C₁–C₄ alkyl, C₁–C₄ alkoxy,    methylenedioxy or amino radical; a radical

-    in which m and n are integers, which may be identical or different,    between 0 and 3 inclusive, X represents an oxygen atom or an NH    group, Y represents a hydrogen atom or a C₁–C₄ alkyl radical, and Z    represents a methyl radical when n is equal to 0, or Z represents a    C₁–C₄ alkyl radical, a group OR or NR″R′″ when n is greater than or    equal to 1, R″ and R′″, which may be identical or different,    denoting a hydrogen atom or a C₁–C₄ alkyl radical; or R₉ forms with    the nitrogen atom of the group NR₇R₈ in position 5 an at least    4-membered heterocycle,-   R₆ represents a C₁–C₆ alkyl radical; a C₁–C₄ hydroxyalkyl radical; a    C₁–C₄ aminoalkyl radical; a (C₁–C₄)alkylamino(C₁–C₄)alkyl radical; a    di(C₁–C₄)alkylamino(C₁–C₄)alkyl radical; a    hydroxy(C₁–C₄)alkylamino(C₁–C₄)alkyl radical; a (C₁–C₄)alkoxymethyl    radical; a phenyl radical; a phenyl radical substituted with a    halogen atom or with a C₁–C₄ alkyl, C₁–C₄ alkoxy, nitro,    trifluoromethyl, amino or C₁–C₄ alkylamino radical; a benzyl    radical; a benzyl radical substituted with a halogen atom or with a    C₁–C₄ alkyl, C₁–C₄ alkoxy, nitro, trifluoromethyl, amino or C₁–C₄    alkylamino radical; a heterocycle chosen from thiophene, furan and    pyridine, or a radical —(CH₂)_(p)—O—(CH₂)_(q)—OR″, in which p and q    are integers, which may be identical or different, between 1 and 3    inclusive and R″ is as defined above, it being understood that:-   at least one of the radicals R₁, R₂, R₃ and R₄ represents a hydrogen    atom.

Among the triaminopyrazoles that are useful as oxidation bases in thedye compositions in accordance with the invention, mention may be mademore particularly of the compounds of formula (III) below, and theaddition salts thereof with an acid:

in which:

-   R₇ and R₈, which may be identical or different, represent a hydrogen    atom or a C₁–C₄ alkyl or C₂–C₄ hydroxyalkyl radical.

Among the 4,5- or 3,4-diaminopyrazoles of formula (I) above that may bementioned more particularly are4,5-diamino-1-(4′-methoxybenzyl)pyrazole,4,5-diamino-1-(4′-methylbenzyl)pyrazole,4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1-(3′-methoxybenzyl)pyrazole,4-amino-1-(4′-methoxybenzyl)-5-methylaminopyrazole,4-amino-5-(β-hydroxyethyl)amino-1-(4′-methoxybenzyl)pyrazole,4-amino-5-(β-hydroxyethyl)amino-1-methylpyrazole,4-amino-(3)-5-methylaminopyrazole, 3-(5),4-diaminopyrazole,4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole,4,5-diamino-1-isopropylpyrazole, 4,5-diamino-1-hydroxyethylpyrazole,4,5-diamino-1-benzylpyrazole,4-diamino-5-hydroxyethylamino-1-hydroxyethylpyrazole,4-diamino-5-methylamino-1-hydroxyethylpyrazole,3-amino-4,5,7,8-tetrahydropyrazolo[1,5-a]pyrimidine,7-amino-2,3-dihydro-1H-imidazole[1,2-b]pyrazole,3-amino-8-methyl-4,5,7,8-tetrahydropyrazolo[1,5-a]-pyrimidine,2-(4,5-diamino-1-pyrazolyl)-1-ethanesulphonic acid,2-(4,5-diamino-1-pyrazolyl)acetamide, 2-(4,5-diamino-1-pyrazolyl)aceticacid, 2-(2-dimethylaminoethyl)-2H-pyrazole-3,4-diamine and2-(2-methoxyethyl)-2H-pyrazole-3,4-diamine, and the addition saltsthereof with an acid.

The diaminopyrazoles that are useful in the present invention may beobtained via synthetic processes that are well known to those skilled inthe art. For example, the 4,5-diaminopyrazoles of formula (II) may beprepared according to the synthetic process as described, for example,in French patent application FR-A-2 733 749.

Among the 4,5-diaminopyrazoles of formula (II) above that may bementioned more particularly are:

-   1-benzyl-4,5-diamino-3-methylpyrazole,-   4,5-diamino-1-(β-hydroxyethyl)-3-(4′-methoxyphenyl)pyrazole,-   4,5-diamino-1-(β-hydroxyethyl)-3-(4′-methylphenyl)pyrazole,-   4,5-diamino-1-(β-hydroxyethyl)-3-(3′-methylphenyl)pyrazole,-   4,5-diamino-3-methyl-1-isopropylpyrazole,-   4,5-diamino-3-(4′-methoxyphenyl)-1-isopropylpyrazole,-   4,5-diamino-1-ethyl-3-methylpyrazole,-   4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,-   4,5-diamino-3-hydroxymethyl-1-methylpyrazole,-   4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,-   4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,-   4,5-diamino-3-hydroxymethyl-1-tert-butylpyrazole,-   4,5-diamino-3-hydroxymethyl-1-phenylpyrazole,-   4,5-diamino-3-hydroxymethyl-1-(2′-methoxyphenyl)pyrazole,-   4,5-diamino-3-hydroxymethyl-1-(3′-methoxyphenyl)pyrazole,-   4,5-diamino-3-hydroxymethyl-1-(4′-methoxyphenyl)pyrazole,-   1-benzyl-4,5-diamino-3-hydroxymethylpyrazole,-   4,5-diamino-3-methyl-1-(2′-methoxyphenyl)pyrazole,-   4,5-diamino-3-methyl-1-(3′-methoxyphenyl)pyrazole,-   4,5-diamino-3-methyl-1-(4′-methoxyphenyl)pyrazole,-   3-aminomethyl-4,5-diamino-1-methylpyrazole,-   3-aminomethyl-4,5-diamino-1-ethylpyrazole,-   3-aminomethyl-4,5-diamino-1-isopropylpyrazole,-   3-aminomethyl-4,5-diamino-1-tert-butylpyrazole,-   4,5-diamino-3-dimethylaminomethyl-1-methylpyrazole,-   4,5-diamino-3-dimethylaminomethyl-1-ethylpyrazole,-   4,5-diamino-3-dimethylaminomethyl-1-isopropylpyrazole,-   4,5-diamino-3-dimethylaminomethyl-1-tert-butylpyrazole,-   4,5-diamino-3-ethylaminomethyl-1-methylpyrazole,-   4,5-diamino-3-ethylaminomethyl-1-ethylpyrazole,-   4,5-diamino-3-ethylaminomethyl-1-isopropylpyrazole,-   4,5-diamino-3-ethylaminomethyl-1-tert-butylpyrazole,-   4,5-diamino-3-methylaminomethyl-1-methylpyrazole,-   4,5-diamino-3-methylaminomethyl-1-isopropylpyrazole,-   4,5-diamino-1-ethyl-3-methylaminomethylpyrazole,-   1-tert-butyl-4,5-diamino-3-methylaminomethylpyrazole,-   4,5-diamino-3-[(β-hydroxyethyl)aminomethyl]-1-methylpyrazole,-   4,5-diamino-3-[(β-hydroxyethyl)aminomethyl]-1-isopropylpyrazole,-   4,5-diamino-1-ethyl-3-[(β-hydroxyethyl)aminomethyl]pyrazole,-   1-tert-butyl-4,5-diamino-3-[(β-hydroxyethyl)aminomethyl]pyrazole,-   4-amino-5-(β-hydroxyethyl)amino-1,3-dimethylpyrazole,-   4-amino-5-(β-hydroxyethyl)amino-1-isopropyl-3-methylpyrazole,-   4-amino-5-(β-hydroxyethyl)amino-1-ethyl-3-methylpyrazole,-   4-amino-5-(β-hydroxyethyl)amino-1-tert-butyl-3-methylpyrazole,-   4-amino-5-(β-hydroxyethyl)amino-1-phenyl-3-methylpyrazole,-   4-amino-5-(β-hydroxyethyl)amino-1-(2-methoxyphenyl)-3-methylpyrazole,-   4-amino-5-(β-hydroxyethyl)amino-1-(3-methoxyphenyl)-3-methylpyrazole,-   4-amino-5-(β-hydroxyethyl)amino-1-(4-methoxyphenyl)-3-methylpyrazole,-   4-amino-5-(β-hydroxyethyl)amino-1-benzyl-3-methylpyrazole,-   4-amino-1-ethyl-3-methyl-5-methylaminopyrazole,-   4-amino-1-tert-butyl-3-methyl-5-methylaminopyrazole,-   4,5-diamino-1,3-dimethylpyrazole,-   4,5-diamino-3-tert-butyl-1-methylpyrazole,-   4,5-diamino-1-tert-butyl-3-methylpyrazole,-   4,5-diamino-1-methyl-3-phenylpyrazole,-   4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,-   4,5-diamino-1-(β-hydroxyethyl)-3-phenylpyrazole,-   4,5-diamino-1-methyl-3-(2′-chlorophenyl)pyrazole,-   4,5-diamino-1-methyl-3-(4′-chlorophenyl)pyrazole,-   4,5-diamino-1-methyl-3-(3′-trifluoromethylphenyl)pyrazole,-   4,5-diamino-1,3-diphenylpyrazole,-   4,5-diamino-3-methyl-1-phenylpyrazole,-   4-amino-1,3-dimethyl-5-phenylaminopyrazole,-   4-amino-1-ethyl-3-methyl-5-phenylaminopyrazole,-   4-amino-1,3-dimethyl-5-methylaminopyrazole,-   4-amino-3-methyl-1-isopropyl-5-methylaminopyrazole,-   4-amino-3-isobutoxymethyl-1-methyl-5-methylaminopyrazole,-   4-amino-3-methoxyethoxymethyl-1-methyl-5-methylaminopyrazole,-   4-amino-3-hydroxymethyl-1-methyl-5-methylaminopyrazole,-   4-amino-1,3-diphenyl-5-phenylaminopyrazole,-   4-amino-3-methyl-5-methylamino-1-phenylpyrazole,-   4-amino-1,3-dimethyl-5-hydrazinopyrazole,-   5-amino-3-methyl-4-methylamino-1-phenylpyrazole,-   5-amino-1-methyl-4-(N,N-methylphenyl)amino-3-(4′-chlorophenyl)pyrazole,-   5-amino-3-ethyl-1-methyl-4-(N,N-methylphenyl)aminopyrazole,-   5-amino-1-methyl-4-(N,N-methylphenyl)amino-3-phenylpyrazole,-   5-amino-3-ethyl-4-(N,N-methylphenyl)aminopyrazole,-   5-amino-4-(N,N-methylphenyl)amino-3-phenylpyrazole,-   5-amino-4-(N,N-methylphenyl)amino-3-(4′-methylphenyl)pyrazole,-   5-amino-3-(4′-chlorophenyl)-4-(N,N-methylphenyl)aminopyrazole,-   5-amino-3-(4′-methoxyphenyl)-4-(N,N-methylphenyl)aminopyrazole,-   4-amino-5-methylamino-3-phenylpyrazole,-   4-amino-5-ethylamino-3-phenylpyrazole,-   4-amino-5-ethylamino-3-(4′-methylphenyl)pyrazole,-   4-amino-3-phenyl-5-propylaminopyrazole,-   4-amino-5-butylamino-3-phenylpyrazole,-   4-amino-3-phenyl-5-phenylaminopyrazole,-   4-amino-5-benzylamino-3-phenylpyrazole,-   4-amino-5-(4′-chlorophenyl)amino-3-phenylpyrazole,-   4-amino-3-(4′-chlorophenyl)-5-phenylaminopyrazole,-   4-amino-3-(4′-methoxyphenyl)-5-phenylaminopyrazole,-   1-(4′-chlorobenzyl)-4,5-diamino-3-methylpyrazole,-   4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,-   4-amino-1-ethyl-3-methyl-5-methylaminopyrazole,-   4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole,    and the addition salts thereof with an acid.

Among the 4,5- or 3,4-diaminopyrazoles of formula (I) above, thefollowing are more particularly preferred:

-   4,5-diamino-1-benzylpyrazole,-   4,5-diamino-1-(4′-chlorobenzyl)pyrazole,-   4,5-diamino-1-methylpyrazole,-   4,5-diamino-1-hydroxyethylpyrazole,-   2-(2-methoxyethyl)-2H-pyrazole-3,4-diamine    and the addition salts thereof with an acid.

Among the 4,5-diaminopyrazoles of formula (II) above, the following aremore particularly preferred:

-   4,5-diamino-1,3-dimethylpyrazole,-   4,5-diamino-3-methyl-1-phenylpyrazole,-   4,5-diamino-1-methyl-3-phenylpyrazole,-   4-amino-1,3-dimethyl-5-hydrazinopyrazole,-   1-benzyl-4,5-diamino-3-methylpyrazole,-   4,5-diamino-3-tert-butyl-1-methylpyrazole,-   4,5-diamino-1-tert-butyl-3-methylpyrazole,-   4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,-   4,5-diamino-1-ethyl-3-methylpyrazole,-   4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,-   4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,-   4,5-diamino-3-hydroxymethyl-1-methylpyrazole,-   4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,-   4,5-diamino-3-methyl-1-isopropylpyrazole,-   4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole,    and the addition salts thereof with an acid.

Among the triaminopyrazoles of formula (III) above that may be mentionedmore particularly are 3,4,5-triaminopyrazole,1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole and3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and the additionssalts thereof with an acid.

The 4,5- or 3,4-diaminopyrazole(s) and/or the triaminopyrazole(s) inaccordance with the invention and/or the corresponding addition salt(s)with an acid preferably represent from 0.0005% to 12% by weightapproximately relative to the total weight of the dye composition andmore preferably from 0.005% to 6% by weight approximately relative tothis weight.

Preferably, the weight ratio of the mineral compound(s) to the 4,5- or3,4-diaminopyrazole(s) and/or the triaminopyrazole(s) and/or theaddition salt(s) with an acid is between 0.001 and 100 and even morepreferably between 0.01 and 10.

The dye compositions in accordance with the invention preferably containat least one coupler. The couplers that may be used are thoseconventionally used for oxidation dyeing, and especiallymeta-phenylenediamines, meta-aminophenols, meta-diphenols, naphtholderivatives and heterocyclic couplers.

The meta-phenylenediamines, meta-aminophenols and meta-diphenols whichmay be used as additional couplers in the dye composition in accordancewith the invention are preferably chosen from the compoundscorresponding to formula (1) below, and the addition salts thereof withan acid:

in which:

-   A and B, which may be identical or different, represent a hydroxyl,    amino or —NHR₂₂ radical in which R₂₂ represents a C₁–C₄ alkyl, C₁–C₄    monohydroxyalkyl or C₂–C₄ polyhydroxyalkyl radical,-   R₁₉, R₂₀ and R₂₁, which may be identical or different, represent a    hydrogen atom or a halogen atom such as a bromine, chlorine, iodine    or fluorine atom, or a C₁–C₄ alkyl, C₁–C₄ alkoxy, C₁–C₄    monohydroxyalkyl, C₂–C₄ polyhydroxyalkyl, C₁–C₄ monohydroxyalkoxy or    C₂–C₄ polyhydroxyalkoxy radical.

Among the compounds of formula (1) above, mention may be made inparticular of 2-methyl-5-aminophenol, 2-methyl-5-amino-6-chlorophenol,5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene and2,6-bis(β-hydroxyethylamino)toluene, and the addition salts thereof withan acid.

The heterocyclic coupler(s) which may be used as additional couplers inthe dye composition in accordance with the invention can be chosen inparticular from indole derivatives, indoline derivatives, pyridinederivatives, pyrimidine derivatives and pyrazolones, and the additionsalts thereof with an acid.

Among these heterocyclic couplers, mention may be made in particular,for example, of sesamol,1-N-(β-hydroxyethyl)amino-3′,4-methylenedioxybenzene, 6-hydroxyindole,4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline,6-hydroxybenzomorpholine, 2,6-dihydroxy-4-methylpyridine,3,5-diamino-2,6-dimethoxypyridine, 2-amino-3-hydroxypyridine,1-H-3-methylpyrazol-5-one and 1-phenyl-3-methylpyrazol-5-one, and theaddition salts thereof with an acid.

Among the naphthol derivatives that may be mentioned are α-naphthol and2-methyl-1-naphthol.

The additional coupler(s) preferably represent(s) from 0.0001% to 10% byweight approximately relative to the total weight of the dyecomposition, and even more preferably from 0.005% to 5% by weightapproximately relative to this weight.

The dye compositions in accordance with the invention may also containother oxidation bases conventionally used for oxidation dyeing, otherthan a diaminopyrazole and a triaminopyrazole and/or direct dyes,especially to modify the shades or to enrich them with glints.

The additional oxidation bases that may be used in the context of thepresent invention are chosen from those conventionally known inoxidation dyeing, and among which mention may be made especially ofortho- and para-phenylenediamines, double bases, ortho- andpara-aminophenols, and heterocyclic bases other than the pyrazoles ofthe invention, and also the addition salts thereof with an acid, andespecially:

-   (I) the para-phenylenediamines of formula (2) below, and the    addition salts thereof with an acid:

-    in which:    -   R_(a) represents a hydrogen atom, a C₁–C₄ alkyl radical, a C₁–C₄        monohydroxyalkyl radical, a C₂–C₄ polyhydroxyalkyl radical, a        (C₁–C₄)alkoxy(C₁–C₄)alkyl radical, a C₁–C₄ alkyl radical        substituted with a nitrogenous group, a phenyl radical or a        4′-aminophenyl radical;    -   R_(b) represents a hydrogen atom, a C₁–C₄ alkyl radical, a C₁–C₄        monohydroxyalkyl radical, a C₂–C₄ polyhydroxyalkyl radical, a        (C₁–C₄)alkoxy(C₁–C₄)alkyl radical or a C₁–C₄ alkyl radical        substituted with a nitrogenous group;    -   R_(c) represents a hydrogen atom, a halogen atom such as a        chlorine atom, a C₁–C₄ alkyl radical, a sulfo radical, a        carboxyl radical, a C₁–C₄ monohydroxyalkyl radical, a C₁–C₄        hydroxyalkoxy radical, an acetylamino(C₁–C₄)alkoxy radical, a        C₁–C₄ mesylaminoalkoxy radical or a carbamoylamino(C₁–C₄)alkoxy        radical,    -   R_(d) represents a hydrogen or halogen atom or a C₁–C₄ alkyl        radical,    -   R_(a) and R_(b) may also form with the nitrogen atom that bears        them a 5- or 6-membered nitrogenous heterocycle optionally        substituted with one or more alkyl, hydroxyl or ureido groups.

Among the nitrogenous groups of formula (2) above, mention may be madein particular of amino, mono(C₁–C₄)alkylamino, di(C₁–C₄)alkylamino,tri(C₁–C₄)alkylamino, monohydroxy(C₁–C₄)alkylamino, imidazolinium andammonium radicals.

Among the para-phenylenediamines of formula (2) above, mention may bemade more particularly of para-phenylenediamine, para-tolylenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N,N-bis(β-hydroxyethyl)-2-methylaniline,4-amino-3-chloro-N,N-bis(β-hydroxyethyl)aniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamineand 2-β-hydroxyethyloxy-para-phenylenediamine, and the addition saltsthereof with an acid.

Among the para-phenylenediamines of formula (2) above,para-phenylenediamine, para-tolylenediamine,2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine and2-chloro-para-phenylenediamine, and the addition salts thereof with anacid are most particularly preferred.

-   (II) the double bases are compounds comprising at least two aromatic    nuclei bearing amino and/or hydroxyl groups.

Among the double bases which can be used as oxidation bases in the dyecompositions in accordance with the invention, mention may be made inparticular of the compounds corresponding to formula (3) below, and theaddition salts thereof with an acid:

in which:

-   Z₁ and Z₂, which may be identical or different, represent a hydroxyl    or —NH₂ radical which may be substituted with a C₁–C₄ alkyl radical    or with a linker arm Y;-   the linker arm Y represents a linear or branched alkylene chain    containing from 1 to 14 carbon atoms, which may be interrupted by or    terminated with one or more nitrogenous groups and/or one or more    hetero atoms such as oxygen, sulphur or nitrogen atoms, and    optionally substituted with one or more hydroxyl or C₁–C₆ alkoxy    radicals;-   R_(e) and R_(f) represent a hydrogen or halogen atom, a C₁–C₄ alkyl    radical, a C₁–C₄ monohydroxyalkyl radical, a C₂–C₄ polyhydroxyalkyl    radical, a C₁–C₄ aminoalkyl radical or a linker arm Y;-   R_(g), R_(h), R_(i), R_(j), R_(k) and R_(l), which may be identical    or different, represent a hydrogen atom, a linker arm Y or a C₁–C₄    alkyl radical;    it being understood that the compounds of formula (3) contain only    one linker arm Y per molecule.

Among the nitrogenous groups of formula (3) above, mention may be madein particular of amino, mono(C₁–C₄)alkylamino, di(C₁–C₄)alkylamino,tri(C₁–C₄)alkylamino, monohydroxy(C₁–C₄)alkylamino, imidazolinium andammonium radicals.

Among the double bases of formula (3) above, mention may be made moreparticularly ofN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diamino-propanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(β-hydroxyethyl),N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the addition saltsthereof with an acid. Among these double bases of formula (3),N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diamino-propanoland 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, or one of the additionsalts thereof with an acid, are particularly preferred.

-   (III) the para-aminophenols corresponding to formula (4) below, and    the addition salts thereof with an acid:

-    in which:    -   R_(m) represents a hydrogen or halogen atom such as fluorine or        a C₁–C₄ alkyl, C₁–C₄ monohydroxyalkyl,        (C₁–C₄)alkoxy(C₁–C₄)alkyl, C₁–C₄ aminoalkyl or        hydroxy(C₁–C₄)alkylamino(C₁–C₄)alkyl radical,    -   R_(n) represents a hydrogen or halogen atom such as fluorine or        a C₁–C₄-alkyl, C₁–C₄ monohydroxyalkyl, C₂–C₄ polyhydroxyalkyl,        C₁–C₄ aminoalkyl, C₁–C₄ cyanoalkyl or (C₁–C₄)alkoxy-(C₁–C₄)alkyl        radical.

Among the para-aminophenols of formula (4) above, mention may be mademore particularly of para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol and4-amino-2-(β-hydroxyethylaminomethyl)phenol, and the addition saltsthereof with an acid.

-   (IV) the ortho-aminophenols that may be used as oxidation bases in    the context of the present invention are chosen especially from    2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene,    2-amino-1-hydroxy-6-methylbenzene and 5-acetamido-2-aminophenol, and    the addition salts thereof with an acid.-   (V) among the heterocyclic bases which can be used as oxidation    bases in the dye compositions in accordance with the invention,    mention may be made more particularly of pyridine derivatives,    pyrimidine derivatives and pyrazole derivatives and the addition    salts thereof with an acid.

Among the pyridine derivatives, mention may be made more particularly ofthe compounds described, for example, in patents GB 1,026,978 and GB1,153,196, such as-2,5-diaminopyridine,2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine and3,4-diaminopyridine, and the addition salts thereof with an acid.

Among the pyrimidine derivatives, mention may be made more particularlyof the compounds described, for example, in patents DE 2 359 399; JP88-169 571; JP 91-10659 or patent application WO 96/15765, such as2,4,5,6-tetraminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidineand 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such asthose mentioned in patent application FR-A-2 750 048, and among whichmention may be made of pyrazolo[1,5-a]pyrimidine-3,7-diamine,2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,pyrazolo[1,5-a]-pyrimidine-3,5-diamine,2,7-dimethylpyrazolo[1,5-a]-pyrimidine-3,5-diamine,3-aminopyrazolo[1,5-a]-pyrimidin-7-ol,3-aminopyrazolo[1,5-a]pyrimidin-5-ol,2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol,2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol,2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol,2-[(7-aminopyrazolo[1,5-a]-pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol,5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine and2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, the additionsalts thereof, and the tautomeric forms thereof, when a tautomericequilibrium exists, and the addition salts thereof with an acid.

According to the present invention, the additional oxidation bases maypreferably represent from 0.0005% to 12% by weight approximatelyrelative to the total weight of the dye composition.

In general, the addition salts with an acid which can be used in thecontext of the dye compositions of the invention (oxidation bases andcouplers) are chosen in particular from the hydrochlorides,hydrobromides, sulphates, tartrates, lactates and acetates.

The medium which is suitable for the dyeing (or the support) generallyconsists of water or of a mixture of water and at least one organicsolvent in order to dissolve the compounds which would not besufficiently soluble in water. By way of organic solvent, mention may bemade, for example, of C₁–C₄ lower alkanols such as ethanol andisopropanol; glycerol; glycols and glycol ethers such as2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether,diethylene glycol monoethyl ether and monomethyl ether, and aromaticalcohols such as benzyl alcohol or phenoxyethanol, similar products andmixtures thereof.

The solvents can be present in proportions preferably of between 1 and40% by weight approximately relative to the total weight of the dyecomposition, and even more preferably between 5 and 30% by weightapproximately.

The pH of the dye composition in accordance with the invention isgenerally between 3 and 12 approximately and preferably between 5 and 11approximately. It may be adjusted to the desired value with the aid ofacidifying or basifying agents commonly used in the dyeing of keratinfibres.

Among the acidifying agents, mention may be made, by way of example, ofinorganic or organic acids such as hydrochloric acid, orthophosphoricacid, carboxylic acids such as tartaric acid, citric acid or lacticacid, and sulphonic acids.

Among the basifying agents that may be mentioned, for example, areaqueous ammonia, alkaline carbonates, alkanolamines such asmonoethanolamine, diethanolamine and triethanolamine and derivativesthereof, sodium hydroxide, potassium hydroxide and the compounds offormula (5) below:

in which R is a propylene residue optionally substituted with a hydroxylgroup or a C₁–C₄ alkyl radical; R₁₇, R₁₈, R₁₉ and R₂₀, which may beidentical or different, represent a hydrogen atom or a C₁–C₄ alkyl orC₁–C₄ hydroxyalkyl radical.

The dye composition in accordance with the invention can also containvarious adjuvants used conventionally in compositions for dyeing thehair, such as anionic, cationic, nonionic, amphoteric or zwitterionicsurfactants or mixtures thereof, anionic, cationic, nonionic, amphotericor zwitterionic polymers or mixtures thereof, inorganic or organicthickeners, antioxidants, penetration agents, sequestering agents,fragrances, buffers, dispersing agents, conditioners, such as, forexample, volatile or non-volatile silicones, which are modified orunmodified, film-forming agents, ceramides, preserving agents andopacifiers.

Needless to say, a person skilled in the art will take care to selectthis or these optional complementary compound(s) such that theadvantageous properties intrinsically associated with the combination inaccordance with the invention is (are) not, or not substantially,adversely affected by the addition or additions envisaged.

The dye composition in accordance with the invention can be in variousforms, such as in the form of liquids, creams or gels or in any otherform that is suitable for dyeing keratin fibres, and especially humanhair.

A subject of the invention is also a process for dyeing keratin fibres,and in particular human keratin fibres such as the hair, using the dyecomposition as defined above.

According to this process, the dye composition as defined above isapplied to the fibres, the colour being developed at acidic, neutral oralkaline pH using an oxidizing agent, this oxidizing agent possiblybeing added just at the time of use to the dye composition or by meansof an oxidizing composition applied simultaneously or sequentially.

According to one particularly preferred embodiment of the dyeing processaccording to the invention, the dye composition described above ismixed, at the time of use, with an oxidizing composition containing, ina medium which is suitable for dyeing, at least one oxidizing agentpresent in an amount which is sufficient to develop a coloration. Themixture obtained is then applied to the keratin fibres and is left tostand on them for about 3 to 60 minutes, preferably about 5 to 40minutes, after which the fibres are rinsed, washed with shampoo, rinsedagain and dried.

The oxidizing agent present in the oxidizing composition as definedabove may be chosen from the oxidizing agents conventionally used forthe oxidation dyeing of keratin fibres, and among which mention may bemade of hydrogen peroxide, urea peroxide, alkali metal bromates,persalts such as perborates, percarbonates and persulphates, andperacids. Hydrogen peroxide is particularly preferred.

The pH of the oxidizing composition containing the oxidizing agent asdefined above is such that, after mixing it with the dye composition,the pH of the resulting composition applied to the keratin fibrespreferably ranges between about 3 and 12 and even more preferablybetween 5 and 11. It is adjusted to the desired value by means ofacidifying or basifying agents usually used for the dyeing of keratinfibres and as defined above.

The oxidizing composition as defined above can also contain variousadjuvants conventionally used in compositions for dyeing the hair and asdefined above.

The dye composition that is applied to the keratin fibres can be invarious forms, such as in the form of liquids, creams or gels or anyother form which is suitable for dyeing keratin fibres, and inparticular human hair.

According to one variant, a composition containing at least the mineralcompound is applied to these fibres in a first stage, and a compositioncontaining at least one diaminopyrazole is applied in a second stage,the application of the composition containing the mineral compound(s)possibly being followed by a rinsing step, the colour being developedusing an oxidizing agent.

Another subject of the invention is a multi-compartment device or dyeing“kit” or any other multi-compartment packaging system, a firstcompartment of which contains the dye composition as defined above and asecond compartment of which contains the oxidizing composition asdefined above. These devices may be equipped with a means for applyingthe desired mixture to the hair, such as the devices described in patentFR-2 586 913 in the name of the Applicant.

According to a different embodiment, the device comprises at least threecompartments, a first compartment that contains the mineral compoundthat is useful for the invention, a second compartment that contains adiaminopyrazole, and a third compartment that contains an oxidizingcomposition.

The examples that follow are intended to illustrate the inventionwithout, however, limiting its scope.

EXAMPLES Dyeing Examples 1 to 4

The dye compositions below, in accordance with the invention, wereprepared (amounts in grams, AM denotes Active Material):

EXAMPLES 1 2 3 4 4,5-Diamino-1β-hydroxyethyl- 0.645 0.645 0.645 0.645pyrazole dihydrochloride (oxidation base) 3-Amino-6-methylphenol 0.3690.369 0.369 0.369 (coupler) Amorphous pyrogenic silica 0.3  — — — soldunder the name Acematt TS 100 by the company Degussa- Hüls (mineralcompound according to the invention) Alumina of small particle size —0.2  — — sold under the name AluminiumoxidC by the company Degussa-Hüls(mineral compound according to the invention) Boehmite as a 75%colloidal — — 0.15 AM — suspension sold under the name Dispersal S bythe company Condea (mineral compound according to the invention) Zincsulphate containing 7 — — — 0.8  molecules of water (mineral compoundaccording to the invention) Common dye support (**) (**) (**) (**)Demineralized water qs 100 g 100 g 100 g 100 g (**) common dye supportcontaining: Oleyl alcohol polyglycerolated with 4.0 g 2 mol of glycerolOleyl alcohol polyglycerolated with 5.69 g A.M. 4 mol of glycerol,containing 78% active material (A.M.) Oleic acid 3.0 g Oleylaminecontaining 2 mol of 7.0 g ethylene oxide, sold under the trade nameEthomeen O12 by the company Akzo Diethylaminopropyl laurylamino- 3.0 gA.M. succinamate, sodium salt, containing 55% A.M. Oleyl alcohol 5.0 gOleic acid diethanolamide 12.0 g Propylene glycol 3.5 g Ethyl alcohol7.0 g Dipropylene glycol 0.5 g Propylene glycol monomethyl ether 9.0 gSodium metabisulphite as an aqueous 0.455 g A.M. solution containing 35%A.M. Ammonium acetate 0.8 g Antioxidant, sequestering agent qsFragrance, preserving agent qs Aqueous ammonia containing 20% NH₃ 10 g

At the time of use, each dye composition above was mixed with an equalamount by weight of an oxidizing composition consisting of a 20-volumesaqueous hydrogen peroxide solution (6% by weight).

Each resulting composition was applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs. The locks of hair werethen rinsed, washed with a standard shampoo and then dried.

In all cases, a strong and resistant red shade, with good harmlessness,is obtained.

Dyeing Examples 5 to 7

The dye compositions below, in accordance with the invention, wereprepared (amounts in grams):

EXAMPLE 5 6 7 4,5-Diamino-1-ethyl-3-methyl- 0.639 0.639 — pyrazoledihydrochloride (oxidation base) 3,4,5-Triaminopyrazole dihydrochloride— — 0.667 (oxidation base) 3-Amino-6-methylphenol (coupler) 0.369 0.3690.369 Boehmite as a 75% colloidal 0.15 AM — 0.15 AM suspension, soldunder the name Dispersal S by the company Condea (mineral compoundaccording to the invention) Zinc sulphate containing 7 molecules — 0.2 — of water (mineral compound according to the invention) Common dyesupport (**) (**) (**) Demineralized water qs 100 g 100 g 100 g (**)common dye support: identical to that of Examples 1 to 4.

At the time of use, each dye composition above was mixed with an equalamount by weight of an oxidizing composition consisting of a 20-volumesaqueous hydrogen peroxide solution (6% by weight).

Each resulting composition was applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs. The locks of hair werethen rinsed, washed with a standard shampoo and then dried.

In the three cases, a strong and resistant shade, with goodharmlessness, is obtained.

1. Composition for the oxidation dyeing of human keratin fibres, and inparticular of human keratin fibres such as the hair, comprising, in amedium that is suitable for dyeing: 4,5-diamino 1-hydroxyethyl pyrazole,and/or the addition salt thereof with an acid and at least one mineralcompound chosen from silicas, aluminium oxides or hydroxides, aluminium,magnesium and iron hydrosilicates alone or as a mixture, and zinc salts;the said composition not containing a combination of an oxidation baseof the 4,5-diaminopyrazole type, a zinc salt and a derivative of1,4-diazacycloheptane or a salt thereof, having the following formula:

in which R¹, R², R³ and R⁴, which may be identical or different, denotea hydrogen, a C₁–C₄ alkyl or hydroxyalkyl, or a C₂–C₄ dihydroxyalkyl; Z¹and Z², which may be identical or different, denote hydrogen, chlorine,fluorine, a C₁–C₄ alkyl, a C₁–C₄ hydroxyalkyl, a C₁–C₄ aminoalkyl, aC₁–C₄ alkoxy, a C₂–C₄ dihydroxyalkyl or an allyl group; R⁵ and R⁶, whichmay be identical or different, denote a hydrogen or a C₁–C₄ alkyl. 2.Composition according to claim 1, characterized in that the silica(s)is(are) chosen from crystalline or microcrystalline silicas andnon-crystalline silicas.
 3. Composition according to claim 2,characterized in that the non-crystalline silica is vitreous silica. 4.Composition according to claim 2, characterized in that thenon-crystalline silica is chosen from amorphous silicas such ascolloidal silicas, silica gels, precipitated silicas and fumed silicas.5. Composition according to claim 1, characterized in that the aluminiumhydroxides are chosen from the compounds of composition Al (OH)₃ and thecompounds of composition AlOOH.
 6. Composition according to claim 1,characterized in that the aluminium oxides are chosen from activatedaluminas and calcined aluminas.
 7. Composition according to claim 6,characterized in that the activated alumina is α alumina.
 8. Compositionaccording to claim 1, characterized in that the hydrosilicates arechosen from kaolinite, dicktite, nacrite, halloysite-endellite,pyrophyllite, beidellite, talc, chrysotile, montmorillonite, saponite,nontronite, sauconite, amesite, chamosite and illite.
 9. Compositionaccording to claim 1, characterized in that the zinc salts are chosenfrom the salts obtained with a mineral acid.
 10. Composition accordingto claim 9, characterized in that the zinc salts are chosen from zincchloride, sulphate, nitrate, orthophosphate, ortho-hydrogen phosphate,ortho-dihydrogen phosphate, carbonate and hydrogen carbonate. 11.Composition according to claim 1, characterized in that the zinc saltsare chosen from the salts obtained with an organic acid.
 12. Compositionaccording to claim 1, characterized in that the mineral compound(s)represent(s) from 0.00001% to 10% by weight approximately relative tothe total weight of the dye composition.
 13. The composition of claim 1,wherein said 4,5-diamino 1-hydroxyethyl pyrazole and/or thecorresponding addition salt(s) with an acid represent from 0.0005% to12% by weight relative to the total weight of the dye composition. 14.The composition of claim 13, wherein said 4,5-diamino 1-hydroxyethylpyrazole and/or the corresponding addition salt(s) with an acidrepresent from 0.005% to 6% by weight relative to the total weight ofthe dye composition.
 15. The composition of claim 1, wherein that theweight ratio of the mineral compound(s) to the 4,5-diamino1-hydroxyethyl pyrazole and/or the addition salt(s) with an acid isbetween 0.001 and
 100. 16. The composition of claim 1, wherein saidaddition salts with an acid are selected from the group consisting ofhydrochlorides, hydrobromides, sulphates, tartrates, lactates andacetates.
 17. The composition of claim 1, further comprising at leastone coupler.
 18. The composition of claim 17, wherein said coupler(s)represent(s) from 0.0001% to 10% by weight approximately relative to thetotal weight of the dye composition.
 19. The composition of claim 1,further comprising at least one additional oxidation base other than thepyrazoles defined in claims 1 to
 12. 20. The composition of claim 19,wherein said additional oxidation base(s) represent(s) from 0.0005% to12% by weight approximately relative to the total weight of the dyecomposition.
 21. The composition of claim 1, wherein it has a pH ofbetween 3 and
 12. 22. The composition of claim 1, wherein it is in theform of liquids, creams or gels or in any other form that is suitablefor dyeing keratin fibres, and especially human hair.
 23. Process fordyeing keratin fibres, and in particular human keratin fibres such asthe hair, comprising the step of applying the composition of claim 1 tosaid fibres, and wherein the colour is revealed at acidic, neutral oralkaline pH using an oxidizing agent.
 24. The process of claim 23,wherein said oxidizing agent is chosen from hydrogen peroxide, ureaperoxide, alkali metal bromates, persalts such as perborates,percarbonates and persulphates, and peracids.
 25. A process for dyeingkeratin fibres, and in particular human keratin fibres such as the hair,comprising the steps of applying to said fibres a composition containingat least one mineral compound as defined in claim 1 in a first stage,applying to said fibres a composition containing said 4,5-diamino1-hydroxyethyl pyrazole as defined in claim 1 in a second stage, theapplication of said composition containing said mineral compound(s)possibly being followed by a rinsing step, and wherein the colour isdeveloped using an oxidizing agent.
 26. A multi-compartment devicecomprising a first compartment containing said dye composition of claim1 and a second compartment containing an oxidizing composition.
 27. Amulti-compartment device comprising a first compartment containing saidmineral compound as defined in claim 1, a second compartment containingsaid 4,5-diamino 1-hydroxyethyl pyrazole as defined in claim 1, and athird compartment containing an oxidizing composition.
 28. Thecomposition of claim 12 wherein the mineral compound(s) represent(s)from 0.001% to 5% by weight approximately relative to the total weightof the dye composition.
 29. The composition of claim 12 wherein themineral compound(s) represent(s) from 0.001% to 3% by weightapproximately relative to the total weight of the dye composition. 30.The composition of claim 15 wherein the weight ratio of the mineralcompound(s) to the 4,5-diamino 1-hydroxyethyl pyrazole and/or theaddition salt(s) with an acid is between 0.001 and 10.